2-ethynylcyclopropane compounds and process for the preparation thereof

ABSTRACT

Novel 2-ethynylcyclopropane compounds having the formula   WHEREIN R1 represents hydrogen atom, a straight or branched lower alkyl group or an aryl group which may be substituted with trifluoromethyl, nitro, halogen, a lower alkyl or a lower alkoxy, R2 and R3 may be the same or different and each represents hydrogen atom, a straight or branched lower alkyl group, a substituted or unsubstituted aryl group or an alkoxycarbonyl group and R4 represents hydrogen atom or a hydrocarbon group such as alkyl, aryl and aralkyl and the salt thereof.

United States Patent [191 Kishida et al. 1

[ Dec. 10, 1974 1 1 Z-ETHYNYLCYCLOPROPANE COMPOUNDS AND PROCESS FOR THEPREPARATION THEREOF [75] Inventors: Yukichi Kishida; Masafumi Yoshimoto;Nohoru lshida, all of Tokyo, Japan [73] Assignee: Sankyo CompanyLimited, Tokyo,

Japan [22] Filed: June 23, 1971 [21] Appl. No.: 156,049

[30] Foreign Application Priority Data June 29, 1970 Japan 45-56798 [52]US. Cl 260/469, 71/106, 71/111, 71/112, 71/113, 71/115, 260/448 R,260/468 P, 260/473 R, 260/475 SC, 260/471 R,

260/514 P, 260/515 R, 260/515 A, 260/515 [51] Int. Cl. C070 69/76 [58]Field of Search 260/520, 515 R, 515 A, 260/473 R, 469, 468 H, 514 H, 475SC [56] References Cited UNITED STATES PATENTS 3,397,223 8/1968 Payne260/464 3,445,499 5/1969 Martel et a1. 260/464 OTHER PUBLICATIONSDYakonov et al., Chem. Abstracts, vol. 58 (1963), page 6703d.

Primary ExaminerJames A. Patten Attorney, Agent, or FirmFlynn & Frishauf5 7] ABSTRACT Novel Z-ethynylcyclopropane compounds having the form a UW CH COOR l 4 c R2 R 12 Claims, No Drawings Z-ETHYNYLCYCLOPROPANECOMPOUNDS AND PROCESS FOR THE PREPARATION THEREOF The term lower alkyl"is intended to represent an alkyl group having from i to carbon atoms.

The products have pharmacological and agricultural properties and areuseful as'anti-inflammatory agents and herbicides or insecticides.

The products are prepared by reacting a propargyl sulfonium salt havingthe formula R1 c e c CH2 s wherein R, is the same as above, Y, and Y maybe the same or different and each represents a straight or branchedlower alkyl group or Y, and Y taken together with the sulfur atom towhich they are attached may form a saturated heterocyclic ring and Xrepresents an anion with an acrylic acid derivative having the formula CGH 00011 3 wherein R R and R, are the same as above in the presence of abase suh as an alkali metal hydride.

This invention relates to novel Z-ethynylcyclopropane compounds and aprocess for the preparation wherein R represents hydrogen atom, astraight or branched lower alkyl group or an aryl group which may besubstituted with trifluoromethyl, nitro, halogen, a lower alkyl or alower alkoxy, Rg and R may be the same or different and each representshydrogen atom, a straight or branched lower alkyl group, a substitutedor unsubstituted aryl group or an alkoxycarbonyl group and R, representshydrogen atom or a hydrocarbon group such as alkyl, aryl and aralk'yland the salt thereof.

The term lower alkyl is intended to represent an alkyl group having fromI to 5 carbon atoms.

It also relates to a process for the preparation of the2-ethynylcyclopropane compounds having the formula (I).

All of the Z-ethynylcyclopropane compounds of this invention are novelcompounds unknown in the prior art. We have unexpectedly found that theyhave a remarkable insecticidal and herbicidal activities. Especiallythey exhibit a potent insecticidal activity for mosquito (Culex pipiensmoleslus) and have a herbicidal effect in dry field forming, forexample, a tomato farm.

Furthermore they exhibit an anti-inflammatory activity and a blood sugarlowering activity and are useful as medicaments.

[t is thus an object of the present invention to provide a new class ofchemical compounds.

It is another object of this invention to provide new insecticidal orherbicidal compositions and new antiinflammatory or blood sugar loweringcompositions; It is a further object of the present invention to providea process for the preparation of chemical compounds which are useful inmedicinal or agricultural area.

The compounds having the formula (I) in which R represents hydrogen atomare in a free carboxylic acid form and may be administered in their freeform or in the form of their alkali or alkaline earth metal salts suchas sodium, potassium, calcium and aluminum salt. The compounds of thisinvention may be compounded and formulated into pharmaceuticalpreparations in unit dosage form for oral or parenteral administrationwith organic or inorganic solid materials or liquids which arepharmaceutically acceptable carriers.

The composition may take the form of tablets, powders, granules,capsules, suspensions, solutions and the X (II) wherein R is the same asabove, Y and Y may be the same or different and. each represents astraight or branched lower alkyl group or Y, and Y taken together withthe sulfur atom to which they are attached may form .a saturatedheterocyclic ring such as tetrahydrothiopl iene and tetrahydrothiopyranand X represents an anionsuch as a halide ion and sulfate ion with anacrylic acid derivative having the formula CH COOR I) wherein R R and Rare the same as above in the presence of a base.-

ln carrying out the present invention, the compounds (II) are contactedwith the compounds (ill) in the presence of a base preferably using asolvent. As a solvent, there may be employed an inert organic solventwithout limitation that would not adversely affect the reaction.Examples of such a solvent include hydrocarbons such as benzene andtoluene; ethers such as dioxane, tetrahydrofuran and diethyl ether; anddimethyl sulfoxide. There may be usually employed ether or dimethylsulfoxide which has a high solubility of the reactants. As the baseemployed as a catalyst in the reaction, there may be used any basewithout limitation that would be generally used informing carbanion.Examalkoxide such as potassium tertiary butoxide; an alkali metal amidesuch as sodium amide; and a quaternary ammonium base such as Triton B.Most preferable bases are an alkali metal hydride and an alkali metaltertiary alkoxide.

The reaction temperature is not critical but the reaction is desirablycarried out at relatively lower temperature to prevent a side reactionand increase a yield of the desired product. Usually the reaction iscarried out under cooling below C. The reaction period is varied mainlydepending upon the reaction temperature and a kind of the reactant andthe base, but usually about from one hour to about hours. The reactionis preferably carried out in an inert gas atmosphere such as a nitrogenor argon gas atmosphere to prevent an oxidation reaction by oxygen inthe air.

After completion of the reaction, the desired product (I) is separatedfrom the reaction mixture by a conventional means. For instance, aftercompletion of the reaction, the reaction mixture is poured into icewater and the mixture is extracted with a suitable solvent such as ethylacetate.

The extract is washed with saturated aqueous sodium chloride and driedwith a drying agent such as anhydrous sodium sulfate and the solvent isdistilled off to give the desired product. The desired product is, ifnecessary, further purified by distillation or'chromatogra- PM I .1

1n the present invention, there is formed a mixture of cis and transforms of the desired product regarding the ethynyl group and thecarboxyl group attached to the cyclopropane ring.

However only a small amount of the cisform is formed and, therefore, allof the products purified by a conventional means and trans form.

The carboxylic acid compounds having the formula (I) in which R,represents hydrogen atom are alternatively prepared by hydrolyzing thecompound having the formula (I) in which R, represents a hydrocarbongroup with an alkali or alkaline earth metal hydroxide such as sodiumhydroxide and potassium hydroxide. The free carboxylic acid compound maybe, if necessary, converted to alkali or alkaline earth metal salt by aconventional means. For example, the free carboxylic acid compounds arereacted with an alkali or alkaline earth metal alkoxide in alcohol togive the alkali or alkaline earth metal salts.

The propargyl sulfonium salt (ll) is a novel compound and prepared byhalogenating a propargyl alcohol having the formula 1 wherein R, is thesame as above with a phosphorus halogenide'. e.g., phosphorustrichloride, phosphorus tribromide, phosphorus pentachloride andphosphorus pentabromide to give a propargyl halogenide having theformula Y wherein R,is the same as above and X, represents a halogenatom and reacting, the'latter compound with a sulfide having the formulav,-s-v

wherein Y, and Y; are the same as above in a suitable solvent, e.g.,benzene. The above mentioned propargyl alcohol and a process for thepreparation thereof are disclosed in Chem.

Ber. 97, 2118 (1964) and U.'S. Pat. No. 3,332,988.

- PREPARATION OF THE PROPARGYL SULFONIUM SALT (II) [1] Preparation ofo-methylphenylpropargyltetrahydro thiophenium bromide 1. To a mixture of31.2 g. of o-methylphenyl propargyl alcohol, 7.5 ml. of pyridine and 150ml. of anhydrous ether is added dropwise 53.6 g. of phosphorustribromide over minutes while maintaining the temperature between 0-10C. The reaction mixture is stirred at 20C. for 5 hours and poured intoice water. The mixture is extracted with ether and the extract is washedwith aqueous sodium chloride, sodium bicarbonate and aqueous sodiumchloride, successively and dried over anhydrous sodium sulfate. Thesolvent is distilled off and the residue is subjected to distillation togive 26.8 g. of o-methylphenylpropargyl bromide boiling at 95 97C. under0.3 mm. pressure of mercury. The yield is 60.1 percent.

2. 26 g. of o-methylphenylpropargylbromide is ad- 1 mixed with 45 g. oftetrahydrothiophene in 100 m1. of

benzene. The mixture is allowed to stand at room temperature for 15hours. Precipitates thus formed are separated by filtration and washedwith benzene and ether successively to give 30.6 g. ofomethylphenylpropargyltetrahydrothiophenium bromide. The product isfurther purified by recrystallization from a mixture of ethanol andacetone to give pure crystals melting at 108C. The yield is 47.8percent. [11] According to the same procedure as mentioned above, theremay be obtained the following propargyl sulfonium salts:

phenylprop argyltetrahydrothiophenium bromide (m.p.l 28C.),o-chlorophenylpropargyltetrahydrothiophenium bromide (m.p. 122 124C.),

o-methoxyphenylpropargyltetrahydrothiophenium bromide (m.p. 103- 105C.),

m-methylphenylpropargyltetrahydrothiophenium bromide (m.p. 91C.),

m-trifluoromethylphenylpropargyltetrahydrothiophenium bromide (m.p.112C.),

m-chlorophenylpropargyltetrahydrothiophenium bromide (m.p.1l5C.)

m-bromophenylpropargyltetrahydrothiophenium Y bromide (m.p. 115 -1l7C.),

bro-

p-methoxyphenylpropargyltetrahydrothiophenium bromide (m.p. 82C.).

The following examples are presented to further illustrate the presentinvention.

EXAMPLE 1 2Phenylethyny1-1-methoxycarbonylcyclopropane 1. In 50 ml. oftetrahydrofuran are dissolved 2.83 g. of3-phenyl-2-propynyltetrahydrothiophenium bromide and 1.72 g. of methylacrylate and the solution is cooled to 5C. To the solution is added 0.48g. of 50 percent sodium hydride containing mineral oil with stirringwhile introducing argon gas. The reaction mixture is stirred at thattemperature for 30 minutes and further at room temperature for 1 hour.The reaction mixture is poured into 500 ml. of ice water and the mixtureis extracted with ethyl acetate. The extract is washed with saturatedaqueous sodium chloride and dried over anhydrous sodium sulfate and thesolvent is distilled off. The residue is dissolved in acetone and to thesolution is added 20 g. of silica gel. The solvent is uniformlyevaporated to dryness with a rotary evaporator. The residue is put on300 g. of silica gel charged into a chromatography nylon tube of 5 cm.diameter and developed with benzene. When the solvent reaches the bottomof the tube, the development is stopped. The tube is divided into partsand the silica gel of each part is extracted with ethyl acetate. It isconfirmed with thin-layer chromatography that the desired product existsin the middle portion of the tube. The solvent is distilled off from theextract of said part and the residue is subjected to reduced pressuredistillation. The desired product is distilled at 108 110C. under 0.3mm. pressure of mercury. The yield is 1.0 g.

Analysis:

Calculated for 0 5 0 F0 und Mass Spectrum Analysis (M 200.

2. Following the procedure of the above (1), but replacing the3-phenyl-2-propyny1tetrahydrothiophenium bromide with 2.97 g. of3-phenyl-2- propynyltetrahydrothiopyranium bromide, there is obtainedthe desired product.

3. Following the procedure of the above (1), but replacing the3-pheny1-2-propyny1tetrahydrothiophenium bromide with 2.90 g. ofdimethy1-3-phenyl-2- propynylsulfonium bromide, there is obtained thedesired product.

4. In ml. of dimethyl sulfoxide is dissolved potassium tertiary butoxideobtained from 1.76 g. of metallic potassium and tertiary butanol and thesolution is cooled to 0 5C. and stirred vigorously while introducingargon gas. To the resulting mixture is added dropwise a solution of 8.5g. of 3-phenyl-2- propynyltetrahydrothiophenium bromide and 5.2 g. ofmethyl acrylate in 40 m1. of dimethyl sulfoxide. The reaction mixture isstirred at 0 5C. for 30 minutes, allowed to stand overnight and pouredinto 1 1. of ice water. The resulting mixture is extracted with ethylacetate and the extract is treated with the same procedure as in theabove (1 provided that silica gel is used in an amount of three times ofthe above (1) to give 2.8 g. of the desired product.

EXAMPLE 2 2-p-Bromophenylethynyl-1-methoxycarbony1cyclopropane Followingthe procedure of Example l-(l), but replacing the 3-phenyl-2-propynyltetrahydrothiophenium bromide with 3.62 g. of3-pbromophenylethynyltetrahydrothiophenium bromide and replacing thedistillation of the crude product with recrystallization from methanol,there is obtained 1.6 g. of the desired product melting at 57 59C.

IR (liquid film) v em 2235 (c -0) 1734 (ester c=o) g H mm 5 ppm (CD013)1.90 2.20 (2H, multiplet, :0 00-) 1.1 1.6 (2H, multiplet, C CO H ll 3.72(3H,- singlet, -C0OCH5),

Analysis:

Calculated for 0 Found IR (Nujol) V cm O Br 2250 (0E0), (ester c=o)'.

N.M.R. ppm (CD01 2.0 (2H, multiplet, E Ck-Q-L 7.1 e, 7.45 (43, ABquartet, Br

1.35 (2H, multiplet, six-00A a i H v 1 3.73 (3H, singlet, -COOCH yEXAMPLE 3 3-Methyl-2-pheny1ethyny1-l -methoxycarbonylcyclopropaneFollowing the procedure of Example 1-(1), but replacing the methodacrylate with 2.0 g. of methyl crotonate, there is obtained the desiredproduct boiling at 110C. under 0.3 mm pressure of mercury.

5C. To the solution is added 2.40 g. of percent sodium hydridecontaining mineral oil with stirring while introducing nitrogen gas. Thereaction mixture is stirred at that temperature for 30 minutes andfurther at room temperature for 2 hours. It is shaken together with anequivalent volume of ethyl acetate and saturated aqueous sodiumchloride. The organic layer is Analysis:

Calculated for 0 11 0 -0,778.48; H,6.59 Found ens-.25; H,6.24.

IR (liquld filinh/cm N.M.R. 5 ppm (0001 2.2 (1H, mul tiplet, a

(ester c=o) 3 7O (3H, singlet EXAMPLE 42-(1-Propyny1)-l-methoxycarbonylcyclopropane In 250 ml. oftetrahydrofuran are dissolved 1 1.1 g. of 2-butynyltetrahydrothiopheniumbromide and 8.61 g. of methyl aerylate and the solution is cooled to0separated and washed with saturated aqueous sodium chloride and driedover anhydrous sodium sulfate and the solvent is distilled off. Theresidue is subjected to reduced pressure distillation to give 4.0 g. ofthe desired product boiling at 108 110C. under 50 mm. pressure ofmercury.

Analysis:

Mass Spectrum Analysis (M 8 o 2 1 9-54; Hs7-50 Calculated for C H O F0und IR (liquid film) /cm 1735 (ester 0:0)

N.M.R. '5 ppm (CD613) 1.6 2.1 (2H, multiplet,

l-75 (5H, doublet,

0-9 1.6 (2H, multiplet, CYCO 5.68 (5H, singlet,

EXAMPLE 5 2-( l-Propynyl)- l -methoxycarb0nyl-3-methylcyclopropane l.Following the procedure of Example 4, but replacing the methyl acrylatewith 10.0 g. of methyl croton-' ate, there is obtained 2.5 g. of thedesired product boiling at 106 108C. under '20 mm. pressure of mercury.

Analysis:

Calculated for C H Found Mass Spectrum Analysis (M 152.

IR (liquid film) wcm COOCli 9 0 C,7l.ll; H,7.96

: C,72.l0; H,8.29.

: 1732 (ester C= O) N.M.R.. 5 ppm (CD013) 1, .20 (2H, multiplet,so-gi-co) 1.78 H, doublet, J=1.o, 0H c 0X) 1.21 (3H, doublet, J 4.6,CYCO l.O 1.5 (1H,

5-67 (3H, s'lnglet,

2. Following the procedure of the above (I but reacting at 16 -0 18C,there is obtained 3.16 g. of the desired product.

EXAMPLE 6 Z-Ethynyll -methoxycarbonylcyclopropane The reaction iscarried out following the procedure of Example 4. but replacing the2-butynyltetrahydro- OH, H M? multipleb, 67-00 CH H COOCH3) Analysis:

Found Calculated for C7H8O2: C,67.73; H,6.5O.

(liquid film) {cm 2100 (020), 1755 (ester 0:0)

1.6 2.1 (2H, multiplet, 50%00 1.89 (1H, doublet, g-C CY) N.M.R. Sppm (CDG1 1.0 1.6 (2H, multiplet, :CvCO

ii i

3.72 (5H, singlet, COO:3).

EXAMPLE 7 EXAMPLE 9 Z-Phenylethynyl-l-ethoxycarbonylcyclopropane.

Following the procedure of Example l-(l), but replacing the methylacrylate with ethyl acrylate, there is 2- 1 th ll b l obtained l.l g. ofthe desired product as oil. p Bromopheny e yny car oxycyc opropane Thereaction is carried out following the procedure of Example l-(l), butreplacing the 3-phenyl-2- hydrochloric acid andyextracted with ethylacetate.

Analsiitl M C H o I propynyltetrahydrothiophenium bromide, the methyl331; or f Q IZ I :22;: acrylate and the 0.48 g. of 50 percent sodiumhydride Mass pc ctrum Analysis (M) :214. with 3.62 of3-bornophenyl-2-propynyltetrahydrothio- 'ggf i gz g' i (ester C=O)phenium bromide, L44 g. of acrylic acid and 1.44 g. of

50 percent sodium hydride, respectively, and the reac- EXAMPLE 8 25 tionmixture is treated with the same procedure as inZ-Phenylethynyl-l-carboxycyclopropane Example 8 to give 1.6 g. of thedesired product melting The reaction is carried out following theprocedure at 122 124C.

Analysis:

Calculated for C l-0 8R 2 C,54.36; H,3.48; Br,30.6l. Found Q5435; H.307;Br,29.98.

IR (NujoH-ycm" 2230 (C I C), 1710 (C=O), 2550 2780 (OH).

of Example l-( l but replacing the methyl acrylate EXAMPLE 10 and the0.48 g. of 50 percent sodium hydride with 1.44 g g. of acrylic acid and1.44 g. of 50 percent sodium hy- 2-( l-Propynyl)-l-carboxycyclopropanedride, respectively. The reaction mixture is poured into The reaction iscarried out following the procedure ice water and the mixture is madeacidic-by addition of of Example 4, but replacing the methyl acrylateand the 2.40 g. of 50 percent sodium hydride with 7.2 g. of

After the extract is dried over anhydrous sodium sul- 4O acrylic acid,and 7.20 g. of percent sodium hydride fate, the solvent is distilledoff. The crystalline residue respectively, and thereaction mixture istreated with is recrystallized from n-heptane to give l g. of the 'dethesame procedure as in Example 8 to give 2.5 g. of the sired productmelting at 89 C. desired product melting at 87- 88C.

Analysis;

Calculated for C H O C, 77 40; H, 5 41 Found C,77.62; H,5.51.

In (Nujol) a 2230 (C O) 1690 (c=0) 2550 2800 (OH) N.M. R. 5 ppm (CD011.85. 2.25 (2H, multiplei EC7CO-) H .12 7.3 (5H,. multiplet, LI

1.? 1.! (2H, multiplet, -C7-CO),

1.2.0 (11;, :xi n31 at, 400g) Analysis:

Calculated 101 C fi O C,e.'/.73; H,6.5O

Found 0,071.14; 11,6.56.

IR (110301) ell-f 1720 (-10) 2550 2800 (OH) H H 11.11.11. ppm (0001. 1.62.1(211, rnultiplet, c icog 1.74 (3H, doublet, J 21.0, ori -0:04,

11.5 (1H, singlet, COOH).

' EXAMPLE 1 l 56C. The product may be purified by reduced pressuredistillation. (It is distilled at a bath temperature of 3-Methyl-2-(l-propynyl)-l-carboxycyclopropane C. under 2 mm. pressure of mercury).

Analysis:

Calculated for 0 H 0 0,6954; H,7.30.

Found C,69.22; H,7.2l

1R (11113 1) 1 cm 1695 (0:0) 2550 2800 (OH) 1.76 (3H, doublet, J=2-Q,Gil -0 0%,

Ill

1.20 (3H, doublet, J=4.5,

1.0 1.4 (1H, multiplet, E0 700-),

8.55 (1H, singlet, 400g),

The reaction is carried out following the procedure EXAMPLE 12 OfExample 4, but replacing the methyl acrylate and the 3-Phenylethynyl- I-benzyloxycarbonylcyclopropane 240 of 50 Percent Sodium hydride with -6gof Following the procedure of Example l-(l), but recrotic acid and 7.20g. of 50 percent sodium hydride, placing the methyl acrylate with 3.24g. of benzyl acryrespectively, and the reaction procedure as in Example5 late, there is obtained 1.7 g. of the desired product boil- 8 to give3.l g. of the desired product melting at 54 ing at C. under 0.0l mm.pressure of mercury.

Analysis Calculated for 0 H 0 C {82.58; H, 5 .84

Found 0,8238; H,5.75.

I.R. (liquid film 0111 2220 (C 0 1730 (0:0)

- H H in 100 ml. of tetrahydrofuran are dissolved 3.62 g. J3-(p-bromophenyl)-2-propynyltetrahydrothiophenium i t bromide and-methylcinnamate and the solution is cooled to C. with stirring. To the mixtureis 5 added 0.48 g. of 50 percent sodium hydride The mix 1.40 (2H,multlplet, =C--G 7 ture is stirred at that temperature for 30 minutesand ii H further at room temperature for 1 hour. The reaction mixture istreated with the same procedure as in Exam- 5 .1? (2H, singlet COOCH lple l-( l The pure desired product is obtained without distillationprocedure as colorless oil.

Analysis:

Calculated for C H 0 Br: C,64.24; H,4.26; Br,22.50.

Found C,64.l0; H,4.3l; Br,22.l4.

LR. (liquid filmh) om i 2220 (02c), 1735 (c=o).

N.M.R.5 ppm (01301 2.8 (1H, multiplet, 0%

(2H, multipl-et,

'7.3 (5H, multiplec 3.75 (5H, singlet,-COOCl-I 5. EXAMPLE 14 Y 45 7 3singlet 2"* I 3,3-Dimethyl-2-phenylethynyi-l-ethoxycarbonylcyclopropane,H H. Following the procedure of Example l-(l), but replacing the methylacrylate with 2.56 g. of ethylB,B- EXAMPLE 13 so dimethylacrylate, thereis obtained without distillation Ii-Phenyl-Z-p-bromophenylethynyl-1-procedure 0.2 g. of the pure desired product ascolormethoxycarbonylcyclopropane less oil.

Analysis:

Calculated for C H O 0,7951; H,7.49.

Found C,79.l0; H,7.35. LR. (liquid filmM-i-cnf 22 25 (o= 0), 1737 (c=o).

H H N.M.R.5 ppm (012M 2.0 (2H, multiplet, sly-00 7.25 (5H, multiple -bit 17 l.3 (6H, singlet, CTO-i,

1.25 (3H, triplet, oo -c11 4.07 (2H, quartet,-COO-CH CH EXAMPLE l53-Phenylethynyl-l ,2-bis(methoxycarbonyl)cyclopropane Following theprocedure of Example l-(l), but replacing the methyl acrylate with 2.88g. of dimethyl fumarate, there is obtained without distillationprocedure 0.5 g. of the pure desired product as colorless oil.

Analysis:

Calculated for C H l l4 4 Found I.R. (liquid filnihjcnf N.M.R. (2H,multiplet, 20%) 7.33 (5H, multiplet li .H ll 3.78 (6H, singlet, -co00gEXAMPLE 16 mide, S-p-trifluoromethylphenyl-2-propynyltetrahydrothiophenium bromide,3-pfluorophenyl-Z-propynyltetrahydrothiophenium bromide, phenium3-p-chlorophenyl-2-propynyltetrahydrothiobromide, 3-p-bromophenyl-2- (mp55 57C), 2-p-chlorophenylethynyl-lmethoxycarbonylcyclopropane (oil),2-pbromophenylethynyl-l-methoxycarbonylcyclopropane (m.p. 57 59C.) andZ-p-methoxyphenylethynyl-lmethoxycarbonylcyclopropane (oil),respectively.

EXAMPLE l7 2-Phenylethynyll -carboxycyclopropane 46.7 g.2-phenyl-l-methoxycarbonylcyclopropane and 30 g. of potassium hydroxideand dissolved in a mixture of 120 ml. of water and 480 ml. of methanoland the resulting solution is stirred at room temperature for 15 hours.The reaction mixture is made acidic (below pH 1.0) by addition ofhydrochloric acid and extracted with ethyl acetate. The extract iswashed with saturated aqueous sodium chloride and dried over anhydroussodium sulfate. The solvent is distilled off and the residue isrecrystallized from n-heptane to give 25.1 g. of the desired productmelting at 89 90C. The yield is 57.6 percent.

v methoxycarbonylcyclopropane,

ycyclopropane EXAMPLE 18 Following the procedure of Example 17, butreplacing the Z-phenylethynyl-l-methoxycarbonylcyclopropane withZ-o-methylphenylethynyll methoxycarbonylcyclopropane,2-ochlorophenylethynyll -methoxycarbonylcyclopropane,2-o-methoxyphenyethynyl-l-methoxycarbonylcyclopropane,Z-m-methylphenylethynyl-l methoxycarbonylcyclopropane,2-mtrifluoromethylphenylethynyll -methoxycarbonylcyclopropane,2-m-chlorophenylethynyl-lmethoxycarbonylcyclopropane,2-mbromophenylethynyl-l-methoxycarbonylcyclopropane,2-m-methoxyphenylethynyll -methoxycarbonylcyclopropane,2-p-methylphenylethynyl-l-2-ptrifluoromethylphenylethynyl-l-methoxycarbonylcyclopropane,Z-p-fluorphenylethynyll methoxycarbonylcyclopropane,2-pchlorophenylethynyl-l -methoxycarbonylcyclopropane,Z-p-bromophenylethynyl-l-methoxycarbonylcyclopropane and2-p-methoxyphenylethynyl-lmethoxycarbonylcyclopropane, respectively,there are obtained,

2-o-methylphenylethynyl-l-carboxycyclopropane (m.p. 87 89C.),2-ochlorophenylethynyl-l-carboxycyclopropane (m.p. 96.5 980C), 2-0-methoxyphenylethynyl-l-carboxycyclopropane (m.p. 106 108C),2-m-methylpheny1ethynyl-l-carbox- (m.p. 100 102C.),2-mtrifluoromethylphenylethynyl-l-carboxycyclopropane (m.p. 9l- 93C.),2-m-chlorophenylethynyl-l-carboxycyclopropane (m.p. 109 112C),2-mbromophenylethynyll -carboxycyclopropane (m.p. 116 117.5C.),Z-m-methoxyphenylethynyl-1- carboxycyclopropane (oil),Z-p-methylphenylethynyll-carboxycyclopropane (m.p. l 106C),2-ptrifluoromethylphenylethynyll -carboxyclopropane (m.p. l55- 158C),2-p-fluorophenylethynyl-1- carboxycyclopropane (m.p. 99 100C),2-pchlorophenylethynyll -carboxycyclopropane (m.p. 1 14 l 15C.),'Z-p-bromophenylethynyl-l-carb0xycyclopropane (m.p. 122 124C.) and2-pmethoxyphenylethynyl-l-carboxycyclopropane (m.p. 125 128C),respectively.

EXAMPLE l9 Z-Phenylethynyl-l-carboxycyclopropane sodium salt In 10 ml.of absolute ethanol is dissolved 4.14 g. of2-phenylethynyl-l-carboxycyclopropane. The solution is added dropwise toa sodium ethoxide solution prepared from 0.51 g. of sodium and 50.0 ml.of absolute ethanol under cooling with ice. After stirring for 2 hoursthe white precipitates formed are separated by filtration, washed anddried. The crude product is recrystallized from ethanolether to give 2.9g. of the desired product melting at 273 276C. (with decomposition). Theyield is 63 percent.

What is claimed is:

1. A compound having the formula wherein R is a phenyl group of a phenylgroup substituted with a trifluoromethyl, halogen, a lower alkyl, or alower alkoxy group, R and R are the same or different and eachrepresents a hydrogen atom or a phenyl group, and R represents ahydrogen atom, a lower alkyl group or benzyl group, and an alkali metal,an alkaline earth metal or an aluminum salt thereof.

2. 2-Phenylethynyl-l-carboxycyclopropane of the formula of claim I.

3. Z-Phenylethynyl-l-methoxycarbonylcyclopropane of the formula of claim1.

4. 2-p-Bromophenylethynyl-l-methoxycarbonylcyclopropane of theformula ofclaim 1.

5. 3-Methyl-2-phenylethynyl-l-rnethoxycarbonylcyclopropane of theformula of claim 1.

6. Z-Phenylethynyl-l-ethoxycarbonylcyclopropane of the formula of claim1.

7. Z-p-Bromophenylethynyl-l-carboxycyclopropane of the formula of claim1.

8. 3Phenylethynyl-1-benzyloxycarbonylcyclopropane of the formula ofclaim 1.

9. 3-Phenyl-2--p-bromophenylethynyl-1- methoxycarbonylcyclopropane ofthe formula of claim 1.

l0. 3,3-Dimethyl-Z-phenylethynyl-l-ethoxycarbonylcyclopropane of theformula of claim 1.

ll. 3-Phenylethynyl-1,2-bis(methoxycarbonyl)cyclopropane of the formulaof claim 1.

l2. 2-Phenylethynyl-l-carboxycyclopropane sodium salt of the formula ofclaim 1.

1. A COMPOUND HAVING THE FORMULA 2.2-Phenylethynyl-1-carboxycyclopropane of the formula of claim 3.2-Phenylethynyl-1-methoxycarbonylcyclopropane of the formula of claim 1.4. 2-p-Bromophenylethynyl-1-methoxycarbonylcyclopropane of the formulaof claim
 1. 5. 3-Methyl-2-phenylethynyL-1-methoxycarbonylcyclopropane ofthe formula of claim
 1. 6. 2-Phenylethynyl-1-ethoxycarbonylcyclopropaneof the formula of claim
 1. 7.2-p-Bromophenylethynyl-1-carboxycyclopropane of the formula of claim 1.8. 3Phenylethynyl-1-benzyloxycarbonylcyclopropane of the formula ofclaim
 1. 9.3-Phenyl-2-p-bromophenylethynyl-1-methoxycarbonylcyclopropane of theformula of claim
 1. 10.3,3-Dimethyl-2-phenylethynyl-1-ethoxycarbonylcyclopropane of the formulaof claim
 1. 11. 3-Phenylethynyl-1,2-bis(methoxycarbonyl)cyclopropane ofthe formula of claim
 1. 12. 2-Phenylethynyl-1-carboxycyclopropane sodiumsalt of the formula of claim 1.